WO2008052661A1 - Recovery of non-ferrous metals from by-products of the zinc and lead industry using electric smelting with submerged plasma - Google Patents
Recovery of non-ferrous metals from by-products of the zinc and lead industry using electric smelting with submerged plasma Download PDFInfo
- Publication number
- WO2008052661A1 WO2008052661A1 PCT/EP2007/009023 EP2007009023W WO2008052661A1 WO 2008052661 A1 WO2008052661 A1 WO 2008052661A1 EP 2007009023 W EP2007009023 W EP 2007009023W WO 2008052661 A1 WO2008052661 A1 WO 2008052661A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zinc
- residues
- process according
- metals
- oxidizing gas
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/28—Obtaining zinc or zinc oxide from muffle furnace residues
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
- C22B4/005—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys using plasma jets
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/16—Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
- C22B9/22—Remelting metals with heating by wave energy or particle radiation
- C22B9/226—Remelting metals with heating by wave energy or particle radiation by electric discharge, e.g. plasma
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- This invention relates to a single-step pyrometallurgical process for the recovery of non-ferrous metals from zinc bearing residues, in particular from by-products of the zinc and lead industry such as goethite and jarosite.
- the Waelz process is probably the most widely used process for the treatment of EAF-dusts and zinc leach residues.
- a dried mixture of residue, coke and fluxes is fed to a large rotary kiln and heated to 1200-1300 0 C.
- the zinc ferrites are decomposed, and volatile species such as Zn and PbS are fumed.
- the fumes are reoxidized above the bath to form solid particles that can be filtered from the off-gases.
- the recovered ZnO particles can for example be used as a substitute for the calcine in a hydrometallurgical Zn flow sheet.
- the rotary kiln that is used in the Waelz process is a large installation with high investment and operating costs. Moreover, the energy efficiency it rather low and the coke consumption high.
- Coke packed bed reactors such as in the SKF Plasmadust® process are a third option to treat zinc containing residues and EAF dusts in particular.
- an oxidic waste is injected in powdered form through tuyeres in the lower part of the furnace, together with powdered coal and slag formers.
- Energy is provided by plasma torches connected to the tuyeres.
- the rising gases containing the zinc fumes are further reduced and cooled in the packed coke bed and the zinc is recovered in a splash condenser.
- the high energetic needs make the process only economically viable in regions with cheap electricity.
- Another major drawback is that the feed material has to be injected through the tuyeres in powdered form.
- Lead blast furnace slags are normally treated in conventional batch slag fuming operations. The process is carried out in water-cooled jackets and involves the injection of fine pulverized coal and air through tuyeres into the molten slag. Zinc, lead and some other elements are fumed from the slag and reoxidized above the bath to generate oxide particles that are captured in the filter.
- a top-blowing submerged lance furnace (Isasmelt® or Ausmelt®) can also be used to treat zinc containing waste products. Dried residue, coal and fluxes are fed into a first submerged lance furnace, the smelting furnace, to remove part of the zinc and lead from the slag and to remove sulfur. The molten slag continuously overflows into a second submerged lance furnace furnace, the fuming furnace, to adequately remove zinc and lead from the slag to levels down to 3 % . An even lower amount of zinc in the slag is feasible, but coupled with significantly increased operating costs. The amount of coal needed is very high. The need for two furnaces furthermore increases investment costs considerably.
- a last method of treating zinc containing residues is by using DC arc furnaces in which heat is generated by a transferred electric arc from an electrode to the bath.
- the Enviroplas® process for example treats lead blast furnace slag, EAF dusts, and neutral leach residues.
- a reducing agent such as metallurgical coal, charcoal or other carbonaceous material low in moisture and volatiles is again employed for reducing and volatilizing zinc and lead.
- the high tapping temperature of about 1450 °C insures low residual zinc concentrations in the slag, but also causes the refractory lining to degrade rapidly.
- a novel process is proposed, which overcomes most of the above drawbacks.
- the process requires only a single step, combining an oxidizing submerged-plasma flame with an addition of a solid reductant to the top of the slag.
- the invented process for the recovery of metals from industrial Zn residues containing Zn, Fe and S, wherein Zn is fumed, Fe is slagged, and S is oxidized to SO 2 is characterized in that the Zn fuming, the Fe slagging, and the S oxidation are performed in a single step process, by smelting said residues in a furnace comprising at least one submerged plasma torch generating an oxidizing gas mixture, and by feeding a solid reducing agent to the melt.
- At least one submerged plasma torch is preferably of the non- transferred type, whereby the oxidizing gas mixture is injected into the slag phase.
- the oxidizing gas mixture is generated by feeding a mixture of air and a gaseous hydrocarbon to the plasma torch.
- the process is particularly useful for treating industrial Zn residues contain In and/or Ge, leading to the valorization by fuming of these metals. It is also specially adapted for treating goethite.
- the process is most useful when Cu is present in the industrial Zn residues and/or in the solid reducing agent.
- Adapting the oxidizing gas mixture in a way known to the man of the art leads to the formation of a Cu matte phase that preferably contains more than 40 wt.%, or, more preferably, more than 50 wt.% Cu.
- one or more non-transferred DC plasma torches are used as a high intensity heat source.
- the reactor is filled with slag, which is molten down by the plasma tuyeres until these are submerged.
- the plasma is continuously generated in the slag layer.
- the bubbles created by the plasma gas injection create a highly turbulent bath.
- the feed is entered from the top and needs no preparation whatsoever: wet feed material is perfectly acceptable.
- the furnace furthermore makes use of the freeze lining concept: the furnace walls are water cooled and the splashing slag solidifies on the walls, creating an isolating crust that reduces the heat losses.
- the slag composition is chosen in such a way that the process can be operated at high temperatures with a thick freeze lining, meaning that the liquidus temperature of the slag should be high to avoid excessive overheating of the slag.
- the high operating temperatures allow for fast fuming rates without the problem of refractory brick degradation.
- Solid reducing agents such as coal, cokes, electronic scraps, or automobile shredder residue are added to the feed, or reductants such as natural gas, LPG or oil are fed through the tuyeres.
- reductants such as natural gas, LPG or oil are fed through the tuyeres.
- thermodynamics predict it is assumed that this way of operating causes different local thermodynamic zones, which are reducing in the neighborhood of the solid reductants but oxidizing in the neighborhood of the bubbles. These clearly differentiated zones apparently can coexist in one single furnace. As a result, the process succeeds in attaining high fuming rates, generating a high grade matte and a clean, discardable slag.
- the discovery opens up an additional degree of freedom in running the process: the amount of excess oxygen in the plasma flame can be freely tuned, providing only the necessary amount of excess oxygen needed to reach the intended phase compositions. This can be realized by using a mixture of air and a limited amount of a reducing agent such as methane or any other hydrocarbon compound.
- the desired phase compositions typically depend on the composition of the feed materials.
- a high grade matte is normally desired: care must then be taken not to over-oxidize and thereby convert the matte.
- the addition of methane to the plasma gas is in these conditions useful to limit the amount of free oxygen.
- the feed contains e.g. metallic iron, it might be preferred to oxidize it in the process, the required oxygen being then mainly provided by the plasma flame. No methane will be added in this case.
- Another beneficial result from processing goethite or other zinc residues with this technology is that, besides Zn, elements like In and Ge are fumed. They can be valorized in later processing steps. Precious group metals that are typically present in small amounts in the zinc residues will be retrieved in the matte and the fumes. Other products such as paragoethiet, jarosite and leaching residues can also suitable be processed.
- a starting smelt is created by melting a mix of a lead blast furnace (LBF) slag and a recycled slag from earlier tests. Goethite is then fed to the bath, along with plastic scraps as solid reductants. A neutral plasma gas is used, delivering 100 m 3 /h of air, 10 m 3 /h of methane and 16 m 3 /h of nitrogen as swirling gas. The process is carried out as described above. Table 1 shows the composition and amounts of the feed and output materials. Although the test resulted in very low zinc concentration in the produced slag, the matte grade is low.
- Table 1 Compositions (wt.%) and amounts of feed and output materials using a neutral plasma gas
- Table 2 shows the fuming of Indium, resulting in In enriched flue dusts. Fumed In can economically be recovered in further processing steps. A similar valorization can optionally be performed for Ge. Ag, together with other precious metals, is retrieved in the matte and in the flue dusts. It can be valorized using known methods. Table 2: Compositions (wt.%) and amounts of feed and output materials using an oxidizing plasma gas
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2007315330A AU2007315330B2 (en) | 2006-11-02 | 2007-10-18 | Recovery of non-ferrous metals from by-products of the zinc and lead industry using electric smelting with submerged plasma |
EP20070819091 EP2082070A1 (en) | 2006-11-02 | 2007-10-18 | Recovery of non-ferrous metals from by-products of the zinc and lead industry using electric smelting with submerged plasma |
US12/447,930 US7905941B2 (en) | 2006-11-02 | 2007-10-18 | Recovery of non-ferrous metals from by-products of the zinc and lead industry using electric smelting with submerged plasma |
KR1020097011109A KR101383521B1 (en) | 2006-11-02 | 2007-10-18 | Recovery of non-ferrous metals from by-products of the zinc and lead industry using electric smelting with submerged plasma |
JP2009535006A JP5183638B2 (en) | 2006-11-02 | 2007-10-18 | Recovery of non-ferrous metals from zinc and lead industry byproducts using electrothermal smelting in submerged plasma |
CA 2668506 CA2668506C (en) | 2006-11-02 | 2007-10-18 | Recovery of non-ferrous metals from by-products of the zinc and lead industry using electric smelting with submerged plasma |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06022807.9 | 2006-11-02 | ||
EP06022807 | 2006-11-02 | ||
US85682106P | 2006-11-06 | 2006-11-06 | |
US60/856,821 | 2006-11-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008052661A1 true WO2008052661A1 (en) | 2008-05-08 |
Family
ID=38965770
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/009023 WO2008052661A1 (en) | 2006-11-02 | 2007-10-18 | Recovery of non-ferrous metals from by-products of the zinc and lead industry using electric smelting with submerged plasma |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2082070A1 (en) |
JP (1) | JP5183638B2 (en) |
AU (1) | AU2007315330B2 (en) |
CA (1) | CA2668506C (en) |
WO (1) | WO2008052661A1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101906542A (en) * | 2010-08-11 | 2010-12-08 | 云南蓝湾矿业有限公司 | Method for recovering germanium from flyash by wet process |
WO2014046593A1 (en) | 2012-09-21 | 2014-03-27 | Valeas Recycling Ab | Plasma induced fuming |
ITRM20130205A1 (en) * | 2013-04-05 | 2014-10-06 | Ecotec Gestione Impianti S R L | PROCEDURE FOR THE EXTRACTION OF SULFUR AND METALS, IN THE FORM OF OXIDES, USABLE IN THE WAELTZ PROCESS, BY SLUDGE CONTAINING COMPOUNDS OF SULFUR AND OF THESE METALS |
CN104232944A (en) * | 2014-09-05 | 2014-12-24 | 韶关凯鸿纳米材料有限公司 | Process for comprehensively recycling indium from ammonia leaching residues and co-producing zinc oxide |
ITUB20154661A1 (en) * | 2015-10-14 | 2017-04-14 | Ecotec Gestione Impianti S R L | Process for the preparation of a concentrate containing metals, rare metals and rare earths from residues generated in the zinc production chain, and thus obtainable concentrate. |
WO2017064735A1 (en) * | 2015-10-14 | 2017-04-20 | Ecotec Gestione Impianti S.R.L. | A method for producing a concentrate containing metais, rare metals and rare earth metals from residuals generated in the zinc production chain and concentrate obtained by said method |
ITUB20154943A1 (en) * | 2015-10-28 | 2017-04-28 | Ecotec Gestione Impianti S R L | Process for the preparation of a concentrate containing metals, rare metals and rare earths from residues generated in the zinc production chain, and thus obtainable concentrate. |
EP3277852B1 (en) | 2015-04-03 | 2021-04-07 | Metallo Belgium | Improved slag from non-ferrous metal production |
WO2021099598A1 (en) | 2019-11-22 | 2021-05-27 | Metallo Belgium | Improved plasma induced fuming furnace |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL3180453T3 (en) * | 2014-08-14 | 2019-03-29 | Umicore | Process for smelting lithium-ion batteries |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4072503A (en) * | 1974-03-21 | 1978-02-07 | Det Norske Zinkkompani A/S | Thermal treatment of leaching residue from hydrometallurgical zinc production |
GB2094353A (en) * | 1981-03-10 | 1982-09-15 | Skf Steel Eng Ab | Selective reduction of heavy metals |
WO2005031014A1 (en) * | 2003-09-29 | 2005-04-07 | Umicore | Process and apparatus for recovery of non-ferrous metals from zinc residues |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3408809B2 (en) * | 1989-08-24 | 2003-05-19 | オースメルト ピーティーワイ.リミテッド | Smelting of metallurgical waste containing iron compounds and toxic elements |
-
2007
- 2007-10-18 AU AU2007315330A patent/AU2007315330B2/en active Active
- 2007-10-18 WO PCT/EP2007/009023 patent/WO2008052661A1/en active Application Filing
- 2007-10-18 CA CA 2668506 patent/CA2668506C/en active Active
- 2007-10-18 JP JP2009535006A patent/JP5183638B2/en active Active
- 2007-10-18 EP EP20070819091 patent/EP2082070A1/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4072503A (en) * | 1974-03-21 | 1978-02-07 | Det Norske Zinkkompani A/S | Thermal treatment of leaching residue from hydrometallurgical zinc production |
GB2094353A (en) * | 1981-03-10 | 1982-09-15 | Skf Steel Eng Ab | Selective reduction of heavy metals |
WO2005031014A1 (en) * | 2003-09-29 | 2005-04-07 | Umicore | Process and apparatus for recovery of non-ferrous metals from zinc residues |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101906542A (en) * | 2010-08-11 | 2010-12-08 | 云南蓝湾矿业有限公司 | Method for recovering germanium from flyash by wet process |
WO2014046593A1 (en) | 2012-09-21 | 2014-03-27 | Valeas Recycling Ab | Plasma induced fuming |
EP2898106A4 (en) * | 2012-09-21 | 2016-06-15 | Val Eas Recycling Solutions Ab | Plasma induced fuming |
US10006100B2 (en) | 2012-09-21 | 2018-06-26 | Val'eas Recycling Solutions Ab | Plasma induced fuming |
ITRM20130205A1 (en) * | 2013-04-05 | 2014-10-06 | Ecotec Gestione Impianti S R L | PROCEDURE FOR THE EXTRACTION OF SULFUR AND METALS, IN THE FORM OF OXIDES, USABLE IN THE WAELTZ PROCESS, BY SLUDGE CONTAINING COMPOUNDS OF SULFUR AND OF THESE METALS |
WO2014162322A3 (en) * | 2013-04-05 | 2014-11-20 | Ecotec Gestione Impianti S.R.L. | Process for extraction of sulphur and metals, in oxide form, usable in the waeltz process, from muds containing compounds of sulphur and said metals |
CN104232944A (en) * | 2014-09-05 | 2014-12-24 | 韶关凯鸿纳米材料有限公司 | Process for comprehensively recycling indium from ammonia leaching residues and co-producing zinc oxide |
EP3277852B1 (en) | 2015-04-03 | 2021-04-07 | Metallo Belgium | Improved slag from non-ferrous metal production |
ITUB20154661A1 (en) * | 2015-10-14 | 2017-04-14 | Ecotec Gestione Impianti S R L | Process for the preparation of a concentrate containing metals, rare metals and rare earths from residues generated in the zinc production chain, and thus obtainable concentrate. |
WO2017064735A1 (en) * | 2015-10-14 | 2017-04-20 | Ecotec Gestione Impianti S.R.L. | A method for producing a concentrate containing metais, rare metals and rare earth metals from residuals generated in the zinc production chain and concentrate obtained by said method |
ITUB20154943A1 (en) * | 2015-10-28 | 2017-04-28 | Ecotec Gestione Impianti S R L | Process for the preparation of a concentrate containing metals, rare metals and rare earths from residues generated in the zinc production chain, and thus obtainable concentrate. |
WO2021099598A1 (en) | 2019-11-22 | 2021-05-27 | Metallo Belgium | Improved plasma induced fuming furnace |
Also Published As
Publication number | Publication date |
---|---|
AU2007315330A1 (en) | 2008-05-08 |
EP2082070A1 (en) | 2009-07-29 |
CA2668506A1 (en) | 2008-05-08 |
AU2007315330B2 (en) | 2012-09-27 |
JP5183638B2 (en) | 2013-04-17 |
JP2010508440A (en) | 2010-03-18 |
CA2668506C (en) | 2013-05-28 |
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